U.S. patent number 4,256,846 [Application Number 06/059,430] was granted by the patent office on 1981-03-17 for method of producing flameproof polyisocyanurate foams.
This patent grant is currently assigned to Bridgestone Tire Co., Ltd.. Invention is credited to Hiroshi Kaneda, Takashi Ohashi, Toru Okuyama, Yoshiko Taniguchi, Masako Yoshida.
United States Patent |
4,256,846 |
Ohashi , et al. |
March 17, 1981 |
Method of producing flameproof polyisocyanurate foams
Abstract
A method of producing flameproof polyisocyanurate foams is
disclosed. When the foam is produced by reacting an organic
polyisocyanate with polyols as a modifying agent in the presence of
an isocyanate trimerization catalyst, a blowing agent and other
additives, a combination of particular low molecular weight diols
with particular high molecular weight polyether polyols is used as
the polyol in a special weight ratio and a special total amount per
100 parts by weight of the organic polyisocyanate in the presence
of special combination of an alkali metal salt of a carboxylic acid
and a tertiary amine compound as the catalyst.
Inventors: |
Ohashi; Takashi (Iruma,
JP), Okuyama; Toru (Sagamihara, JP),
Kaneda; Hiroshi (Higashimurayama, JP), Taniguchi;
Yoshiko (Higashimurayama, JP), Yoshida; Masako
(Kodaira, JP) |
Assignee: |
Bridgestone Tire Co., Ltd.
(Tokyo, JP)
|
Family
ID: |
15206778 |
Appl.
No.: |
06/059,430 |
Filed: |
July 20, 1979 |
Foreign Application Priority Data
|
|
|
|
|
Nov 10, 1978 [JP] |
|
|
53/137785 |
|
Current U.S.
Class: |
521/117; 521/131;
521/902; 521/125; 521/176 |
Current CPC
Class: |
C08G
18/7664 (20130101); C08G 18/6674 (20130101); C08G
18/092 (20130101); C08G 18/675 (20130101); C08G
18/163 (20130101); Y10S 521/902 (20130101) |
Current International
Class: |
C08G
18/16 (20060101); C08G 18/66 (20060101); C08G
18/76 (20060101); C08G 18/00 (20060101); C08G
18/09 (20060101); C08G 18/67 (20060101); C08G
018/14 (); C08G 018/20 (); C08G 018/65 () |
Field of
Search: |
;521/117,125,176,131,902 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Cockeram; H. S.
Attorney, Agent or Firm: Sughrue, Rothwell, Mion, Zinn and
Macpeak
Claims
What is claimed is:
1. A method of producing flameproof polyisocyanurate foams by
reacting an organic polyisocyanate with a polyol in the presence of
an isocyanate trimerization catalyst, a blowing agent and other
additives to form an urethane modified polyisocyanurate foam, which
comprises:
(1) using, as said polyol, at least one low molecular weight diol
selected from the group consisting of (a) compounds having the
general formula
wherein n is 2, 3 or 4, (b) compounds having the general formula
##STR5## wherein n is 2 or 3, (c) 2,3,-butane diol and (d)
2-butene-1,4-diol together with at least one high molecular weight
polyether polyol having 2 to 4 hydroxyl groups in its molecule and
a hydroxyl equivalent of 600 to 2,000,
(2) being a weight ratio of the sum of low molecular weight diols
to the sum of high molecular weight polyetherpolyols within a range
of 0.55 to 7.0,
(3) being a total amount of the low molecular weight diols and high
molecular weight polyetherpolyols used as said polyol within a
range of 12.5 to 25 parts by weight per 100 parts by weight of said
organic polyisocyanate, and
(4) using, as said isocyanate trimerization catalyst, a combination
of an alkali metal salt of a carboxylic acid having a carbon number
of 2 to 12 with a tertiary amino compound in case of using said low
molecular-weight (a)-type diol, or a combination of an alkali metal
salt of a carboxylic acid having a carbon number of 2 to 12 with a
dialkylaminoalkyl phenol in case of using said low molecular weight
(b), (c) or (d)-type diol alone.
2. The method as claimed in claim 1, wherein said organic
polyisocyanate is an aromatic polyisocyanate.
3. The method as claimed in claim 1, wherein said organic
polyisocyanate is a polynuclear polyisocyanate having the following
formula ##STR6## wherein n is 0 or an integer of more than 1, or a
mixture thereof.
4. The method as claimed in claim 1, wherein said high molecular
weight polyetherpolyol is selected from polyoxyalkylene glycols
obtained by reacting ethylene oxide, propylene oxide, butylene
oxide or a mixture thereof with a diol such as ethylene glycol,
1,2-propylene glycol, 1,3-propane diol, 1,4-butane diol, 2,3-butane
diol, 1,5-pentane diol, 1,2-hexane diol, diethylene glycol and
dipropylene glycol; polyoxyalkylene triols or polyoxyalkylene
tetraols obtained by reacting ethylene oxide, propylene oxide,
butylene oxide or a mixture thereof with a triol or tetraol such as
glycerin, trimethylol propane, 1,2,6-hexane triol and
pentaerythritol; and polytetramethylene glycol.
5. The method as claimed in claim 1, wherein said weight ratio of
the sum of low molecular weight diols to the sum of high molecular
weight polyetherpolyols is 1.0 to 5.0.
6. The method as claimed in claim 1, wherein said total amount of
low molecular weight diols and high molecular weight
polyetherpolyols used is 14 to 22 parts by weight per 100 parts by
weight of said organic polyisocyanate.
7. The method as claimed in claim 1, wherein said alkali metal salt
of carboxylic acid having a carbon number of 2 to 12 is selected
from the group consisting of potassium acetate, potassium
propionate, potassium 2-ethylhexanoate, potassium caprylate and
mixtures thereof.
8. The method as claimed in claim 1, wherein said tertiary amino
compound is selected from dialkylaminoalkyl phenols; triethylamine;
triazine cyclic derivatives; tetraalkylalkylene diamines;
triethylenediamine and its lower alkyl substituted derivatives; and
mixtures thereof.
9. The method as claimed in claim 1, wherein said dialkylaminoalkyl
phenol is selected from 2,4,6-tris(dimethylaminoethyl)phenol, 2,4-
and 2,6-bis(dimethylaminomethyl)phenols and mixtures thereof.
10. The method as claimed in claim 1, wherein said blowing agent is
a fluorinated and/or chlorinated low-boiling inert solvent.
11. The method as claimed in claim 1, wherein said blowing agent is
trichloromonofluoromethane.
12. The method of claim 8 wherein said triazine cyclic derivative
is N,N',N"-tris(dimethylaminopropyl)-sym-hexahydrotriazine.
Description
This invention relates to a method of producing flameproof
polyisocyanurate foams. More particularly, it relates to a method
of producing urethane modified polyisocyanurate foams, which have
an excellent fireproof property passed Grade 2 incombustibility
(quasi-incombustible material) according to Japanese Industrial
Standard (JIS) A-1321 combustion test for incombustibility of
internal finish material of buildings, by using a combination of
particular polyols as a modifying agent and using a particular
isocyanate trimerization catalyst.
As is well-known, polyisocyanurate foams are produced by reacting
and foaming organic polyisocyanate in the presence of an isocyanate
trimerization catalyst, a blowing agent and, if necessary, a
surfactant. Such foams have a thermal insulating property
substantially equal to that of polyurethane foams and very
excellent thermal resistance and fireproof property, but they are
very friable and are apt to be burst into fragments like popcorn
under an exposure to a flame, so that they are not yet been put to
practical use.
Now, productions of various modified isocyanurate foams have
hitherto been proposed in order to improve the above drawbacks of
the polyisocyanurate foam. For instance, there have been produced
urethane modified isocyanurate foams using a polyol as a modifying
agent, oxazolidone modified isocyanurate foams using an epoxy
compound as a modifying agent, carbodiimide modified isocyanurate
foams containing carbodiimide bonds, and the like. In these
modified isocyanurate foams, however, it has been confirmed that
the fireproof property lowers to a significant degree though it is
attained to solve the drawbacks of the polyisocyanurate foam.
That is, when these modified isocyanurate foams are evaluated by a
fireproof test under very severe conditions such as JIS A-1321
combustion test for the fireproof property of Grade 2
incombustibility (quasi-incombustible material), they do not pass
acceptable standard values of heat release value, fuming factor,
crack and the like. As a result, it is a common sense in the art
that it is impossible to provide materials passing Grade 2
incombustibility up to now.
The inventors have made various studies with respect to the
modification of the isocyanurate foam and as a result, there has
already been proposed a method of producing modified isocyanurate
foams capable of passing Grade 2 incombustibility wherein an
organic silicone surfactant, which is an essential ingredient in
the production of polyisocyanurate foams, is not used at all or may
be added in an amount of not more than 0.2% by weight based on the
organic polyisocyanate (U.S. Patent Application Ser. No.
917,238).
The thus obtained foams certainly have a fireproof property of
Grade 2 incombustibility. However, the rate of closed cells in the
foam is fairly decreased due to the absence or slight presence of
the surfactant and hence the thermal conductivity becomes larger.
Consequently, the thermal insulating property of the foam lowers
considerably.
With the foregoing in mind, the inventors have further made various
studies with respect to the improvement of the above mentioned
method and found out a method of producing flameproof modified
isocyanurate foams which have thermal insulating property and other
physical properties substantially equal to those of the
polyurethane foam and a fireproof property passed Grade 2
incombustibility according to JIS A-1321 combustion test, and as a
result, the invention has been accomplished.
According to the invention, there is provided a method of producing
flameproof polyisocyanurate foams by reacting an organic
polyisocyanate with a polyol in the presence of an isocyanate
trimerization catalyst, a blowing agent and other additives to form
an urethane modified polyisocyanurate foam, which comprises:
(1) using, as said polyol, at least one low molecular weight diol
(hereinafter referred to as A-group diol) selected from the group
consisting of (a) compounds having the general formula
wherein n is 2, 3 or 4, (b) compounds having the general formula
##STR1## wherein n is 2 or 3, (c) 2,3,-butane diol and (d)
2-butene-1,4-diol together with at least one high molecular weight
polyether polyol (hereinafter referred to as B-group
polyetherpolyol) having 2 to 4 hydroxyl groups in its molecule and
a hydroxyl equivalent of 600 to 2,000,
(2) being a weight ratio of the sum of A-group diols to the sum of
B-group polyetherpolyols within a range of 0.55 to 7.0,
(3) being a total amount of A-group diols and B-group
polyetherpolyols used as said polyol within a range of 12.5 to 25
parts by weight per 100 parts by weight of said organic
polyisocyanate, and
(4) using, as said isocyanate trimerization catalyst, a combination
of an alkali metal salt of a carboxylic acid having a carbon number
of 2 to 12 with a tertiary amino compound in case of using
A-(a)-group diol, or a combination of an alkali metal salt of a
carboxylic acid having a carbon number of 2 to 12 with a
dialkylaminoalkyl phenol in case of using A-(b), (c) or (d)-diol
alone.
According to the invention, urethane modified polyisocyanurate
foams satisfying all of the above mentioned properties are first
obtained only by using particular diols selected from the
well-known low molecular weight diols together with specified high
molecular weight polyether polyols in certain limited weight ratio
and total amount to be reacted with the organic polyisocyanate in
the presence of a particular combination of isocyanate
trimerization catalysts. This fact is an unexpected result which
has never been anticipated from the prior art.
The invention develops unique effects by special combination of
well-known polyols and catalyst as mentioned above and is entirely
different from the prior arts partly similar to the invention as
mentioned below.
For instance, there is disclosed in Japanese Patent Laid-Open No.
101,497/73 that more than 85% of the polyisocyanate is trimerized
by using a low molecular weight diol having a molecular weight of
about 50 to 200 together with a polyol having a molecular weight of
more than 200 in the production of the urethane modified
isocyanurate foam. Especially, the low molecular weight diol
includes a part of diols defined in the invention. In this article,
however, only the molecular weight is defined with respect to the
low molecular weight diol and high molecular weight polyol and
particularly, the practically used polyol is a polyol having a
hydroxyl equivalent of not more than 200, which is fairly smaller
than that defined in the invention, and further there is no
limitation relating to the catalyst used. Moreover, it has been
confirmed that the urethane modified isocyanurate foam obtained by
the method of this article does not pass Grade 2 incombustibility
according to JIS A-1321 combustion test owing to large heat release
value and fuming factor but has a fireproof property passing only
about Grade 3 incombustibility.
On the contrary, the inventors have made various investigations
with respect to the polyols and catalyst and found out that in
order to obtain urethane modified polyisocyanurate foams capable of
passing Grade 2 incombustibility, the kinds of low molecular weight
diols, relatively high molecular weight polyether polyols and
catalysts, weight ratio of diols to polyether polyols, total amount
of diols and polyether polyols per organic polyisocyanate, and the
combination of catalysts should be defined as mentioned above.
Accordingly, it is apparent that the invention cannot be
anticipated from Japanese Patent Laid-Open No. 101,497/73 at
all.
In Japanese Patent Laid-Open No. 81,996/73, there is proposed a
miscible liquid solution for the production of urethane modified
isocyanurate foams, comprising a part of low molecular weight diols
as defined in the invention, other polyols and potassium acetate
among metal salts of carboxylic acids as an isocyanate
trimerization catalyst. However, this article is to improve the
miscibility of the ingredients in the solution and is entirely
different from the invention like the case of Japanese Patent
Laid-Open No. 101,497/73. Moreover, when potassium acetate is used
alone as the isocyanate trimerization catalyst, the foams passing
Grade 2 incombustibility cannot be obtained according to the method
of the invention as mentioned below.
In Japanese Patent Application Publication No. 21,440/78, there is
disclosed a method of producing a rigid polymer article wherein a
mixture of (i) about 5 to 60% by weight of a polyol having 2 to 8
functional group and an equivalent of about 30 to 200 and (ii)
about 40 to 95% by weight of a polyether polyol selected from (a) a
polyether diol having an equivalent of about 750 to 2,100, (b) a
polyether triol having an equivalent of about 750 to 1,500 and (c)
a polyether triol having an equivalent of about 1,500 to 2,100
wherein at least 50% of hydroxyl group in the polyether polyol (c)
is a primary hydroxyl group is used as a polyol and then reacted
and foamed with a polyisocyanate in an amount of about 0.1 to 0.5
equivalent per 1 equivalent of the polyisocyanate in the presence
of an isocyanate trimerization catalyst and a blowing agent.
However, this publication is to improve the shock resistance of the
article obtained under given conditions, i.e. under integrated skin
forming conditions in a closed mold and is entirely different from
the invention in the object. Further, the low molecular weight
polyol ingredient used in this publication is entirely different
from the low molecular weight diol defined in the invention and
there is no description relating to the amounts of polyol
ingredients used and kind and combination of catalyst as mentioned
above. In addition, it has been confirmed that when the tertiary
amino compound such as
N,N',N"-tris(dimethylaminopropyl)sym-hexahydrotriazine, which is
described in this publication, is used alone as the isocyanate
trimerization catalyst, foams capable of passing Grade 2
incombustibility cannot be obtained even by using any combination
of polyols as mentioned below.
In British Pat. No. 1,318,925, there is disclosed a method of
producing an urethane modified isocyanurate foam by using a
polyester polyol as a modifying agent and a combination of a
hydroxide and/or salt of an alkali metal and/or alkaline earth
metal dissolved in an organic solvent having a polar hydroxyl group
and 2,4,6-tris(N,N-dimethylaminomethyl)-phenol of a tertiary amino
compound as an isocyanate trimerization catalyst. However, this
patent is to improve the reactivity and cell properties when the
modifying agent is restricted to the polyester polyol though the
catalyst system is partly included in the catalyst combination
defined in the invention, so that this patent is entirely different
from the invention in the technical idea.
As mentioned above, it is apparent that the invention is entirely
different from the prior arts and cannot easily be conceived from
any combination of the prior arts.
The invention will now be described in greater detail with
reference to the accompanying drawings, wherein:
FIG. 1 is a graph showing a range of developing high fireproof
property (shadowed region) according to the invention in the
three-dimensional system wherein y axis represents a weight ratio
of the sum of low molecular weight diols to the sum of high
molecular weight polyether polyols, x axis represents a total
amount (part by weight) of polyols used per 100 parts by weight of
the organic polyisocyanate, and z axis represents an equivalent
ratio (NCO/OH) of the organic polyisocyanate to the total of
polyols calculated from the ratio of the sum of the low molecular
weight diols to the sum of the high molecular weight polyether
polyols and the total amount of polyols used per 100 parts by
weight of the organic polyisocyanate; and
FIG. 2 is a graph showing exhaust temperature curve and fuming
curve of urethane modified polyisocyanurate foams of the invention
and prior art according to JIS A-1321 surface combustion test.
In the production of urethane modified polyisocyanurate foams
according to the invention, it is necessary that the polyol to be
added as a modifying agent is a combination of A-group diol and
B-group polyetherpolyol as defined above. That is, the A-group diol
is at least one low molecular weight diol selected from the group
consisting of (a) diethylene glycol, triethylene glycol and
tetraethylene glycol of the general formula
wherein n is 2, 3 or 4, (b) dipropylene glycol and tripropylene
glycol of the general formula ##STR2## wherein n is 2 or 3, (c)
2,3-butane diol and (d) 2-butene-1,4-diol. When using the low
molecular weight diol other than the above defined diols, there
cannot be obtained urethane modified polyisocyanurate foams capable
of passing Grade 2 incombustibility.
The B-group polyetherpolyol to be used together with the A-group
diol is at least one polyether polyol having 2 to 4 hydroxyl groups
in its molecule and a hydroxyl equivalent of 600 to 2,000. When
using the polyether polyol other than the above defined
polyetherpolyols, there cannot also be obtained foams capable of
passing Grade 2 incombustibility. As the B-group polyetherpolyol,
mention may be made of polyoxyalkylene glycols obtained by reacting
ethylene oxide, propylene oxide, butylene oxide or a mixture
thereof with a diol such as ethylene glycol, 1,2-propylene glycol,
1,3-propane diol, 1,4-butane diol, 2,3-butane diol, 1,5-pentane
diol, 1,2-hexane diol, diethylene glycol and dipropylene glycol;
polyoxyalkylene triols or polyoxyalkylene tetraols obtained by
reacting ethylene oxide, propylene oxide, butylene oxide or a
mixture thereof with a triol or tetraol such as glycerin,
trimethylol propane, 1,2,6-hexane triol and pentaerythritol;
polytetramethylene glycol and the like.
According to the invention, the weight ratio of low molecular
weight diol to high molecular weight polyether polyol should be
within a range of ##EQU1## and the total amount of A-group diols
and B-group polyetherpolyols used should be within a range of 12.5
to 25 parts by weight per 100 parts by weight of the organic
polyisocyanate. When the weight ratio and total amount are beyond
the above defined ranges, the resulting urethane modified
polyisocyanurate foams do not pass Grade 2 incombustibility due to
the degradation of the fireproof property. Moreover, the preferred
weight ratio of the sum of A-group diols to the sum of B-group
polyetherpolyols is within a range of 1.0 to 5.0 and the preferred
total amount of A-group diols and B-group polyetherpolyols used as
the polyol is within a range of 14 to 22 parts by weight per 100
parts by weight of the organic polyisocyanate. In such preferred
ranges, it makes possible to produce urethane modified
polyisocyanurate foams having more improved fireproof property.
In FIG. 1, the requirements for achievement of the invention are
schematized by a three-dimensional system wherein the weight ratio
of the sum (part by weight) of the A-group diols to the sum (part
by weight) of the B-group polyetherpolyols is plotted on y axis,
the total amount (part by weight) of the A-group diols and B-group
polyetherpolyols used as the polyol per 100 parts by weight of the
organic polyisocyanate is plotted on x axis and the equivalent
ratio (NCO/OH) of the organic polyisocyanate to the total polyols
calculated from the weight ratio of the sum of the A-group diols to
the sum of the B-group polyetherpolyols and the total amount of the
polyols per 100 parts by weight of the organic polyisocyanate is
plotted on z axis. The shadowed region of FIG. 1 is a range of
developing the effect of the invention.
The isocyanate trimerization catalyst to be used in the invention
is alkali metal salts of carboxylic acids having a carbon number of
2 to 12 and tertiary amino compounds. The former includes potassium
acetate, potassium propionate, potassium 2-ethylhexanoate,
potassium caprylate and the like or a mixture thereof. The latter
includes dialkylaminoalkyl phenols such as
2,4,6-tris(dimethylaminomethyl) phenol, a mixture of 2,4- and
2,6-bis(dimethylaminomethyl) phenols and the like; triethylamine;
triazine cyclic derivatives such as
N,N',N"-tris(dimethylaminopropyl)-sym-hexahydrotriazine and the
like; tetraalkylalkylene diamines; dimethylethanol amine;
triethylenediamine and its lower alkyl substituted derivatives; and
mixtures thereof.
According to the invention, it is necessary to use the alkali metal
salt of carboxylic acid having a carbon number of 2 to 12 together
with the tertiary amino compound as the isocyanate trimerization
catalyst when the A-(a)-group diol of the general formula
wherein n is 2, 3 or 4 is used as the low molecular weight diol.
When the alkali metal salt of carboxylic acid or the tertiary amino
compound is used alone, there cannot be obtained urethane modified
polyisocyanurate foams having a favorable fireproof property.
Moreover, the flameproof foams cannot similarly be obtained even
when using an isocyanate trimerization catalyst other than the
above defined catalysts.
When the A-(b), (c) and (d)-diols, i.e. (b) dipropylene glycol and
tripropylene glycol of the general formula ##STR3## wherein n is 2
or 3, (c) 2,3-butane diol and (d) 2-butene-1,4-diol are only used
alone or in admixture thereof together with the B-group
polyetherpolyols as the polyols, the foams having an improved
fireproof property are obtained only by using as the isocyanate
trimerization catalyst the alkali metal salt of carboxylic acid
having a carbon number of 2 to 12 together with a dialkylaminoalkyl
phenol as the tertiary amino compound. In other words, when using
the tertiary amino compound other than the dialkylaminoalkyl
phenols, it makes impossible to produce foams having the desired
fireproof property.
The amount of the isocyanate trimerization catalyst added varies
depending upon the kind of the modifying agent, but it is usually
about 0.5 to 8 parts by weight per 100 parts by weight of the
organic polyisocyanate.
In the production of the urethane modified polyisocyanurate foams
according to the invention, any of organic polyisocyanates used in
the prior art may be used. The organic polyisocyanate means an
organic compound having two or more isocyanate groups in its
molecule and includes aliphatic polyisocyanates, aromatic
polyisocyanates, mixtures and modified substances thereof. As the
aliphatic polyisocyanate, mention may be made of hexamethylene
diisocyanate, isophorone diisocyanate, dicyclohexylmethane
diisocyanate, methylcyclohexane diisocyanate and the like. As the
aromatic polyisocyanate, mention may be made of tolylene
diisocyanate (2,4- and/or 2,6-isomers), diphenylmethane
diisocyanate, ditolylene diisocyanate, naphthalene diisocyanate
(e.g., 1,5-naphthalene diisocyanate), triphenylmethane
triisocyanate, dianisidine diisocyanate, xylylene diisocyanate,
tris(isocyanate phenyl) thiophosphate, polynuclear polyisocyanate
having the following formula ##STR4## wherein n is 0 or an integer
of 1 or more (so-called crude MDI or polymeric isocyanate) obtained
by reacting a low polycondensate of aniline and formaldehyde with
phosgene, undistilled tolylene diisocyanate and the like. Further,
prepolymers having two or more isocyanate groups, which are
obtained by any conventional method, for example, prepolymers
having an urethane group, a biuret group, an isocyanurate group, a
carbodiimide group, an oxazolidone group or the like may be used.
These polyisocyanates may be used alone or in admixture of two or
more polyisocyanates. As the organic polyisocyanate, the aromatic
polyisocyanates, particularly polynuclear aromatic polyisocyanates
are preferable in view of flameproofing.
According to the invention, all of blowing agents used in the
production of conventional polyurethane foams and polyisocyanurate
foams may be used. For instance, the blowing agent includes carbon
dioxide gas generated by adding water to the reaction mixture or
supplied from an external source, nitrogen gas and a mixture
thereof. However, the preferred blowing agent is a low-boiling
inert solvent evaporating by a heat of reaction in the foaming
process. Such a solvent is a fluorinated and/or chlorinated
hydrocarbon having a good compatibility, a typical example of which
includes trichloromonofluoromethane, dichlorodifluoromethane,
dichloromonofluoromethane, monochlorodifluoromethane,
dichlorotetrafluoroethane, 1,1,2-trichloro-1,2,2-trifluoroethane,
methylene chloride, trichloroethane and the like. Further, benzene,
toluene, pentane, hexane and so on may be used. These blowing
agents may be used alone or in an admixture thereof. Among them,
trichloromonofluoromethane is preferable as the blowing agent in
view of the foam properties, easiness of foaming and the like. The
addition amount of the blowing agent is preferably 5 to 50% by
weight of the foam forming composition.
In addition to the above mentioned ingredients, a surfactant and
other additives may be added, if necessary.
As the surfactant, use may be made of any ones usually used in the
production of polyurethane foams and polyisocyanurate foams, an
example of which includes an organosilicone surfactant such as
organopolysiloxanepolyoxyalkylene copolymer, polyalkenyl siloxane
having a side chain of polyoxyalkylene and the like. Further,
oxyethylated alkyl phenol, oxyethylated aliphatic alcohol,
ethylene-propylene oxide block polymer and so on are effective as
the surfactant. The surfactant is usually used in an amount of
about 0.01 to 5 parts by weight per 100 parts by weight of the
organic polyisocyanate.
As the other additive, there are inorganic hollow particles,
granulated refractory, fibrous materials, inorganic fillers and the
like, which are used for improving the foam properties such as
hardness and the like. The inorganic filler includes mica powder,
finely divided clay, asbestos, calcium carbonate, silica gel,
aluminum hydroxide, calcium hydroxide, magnesium hydroxide, gypsum,
sodium silicate and the like.
Moreover, a flame retardant may be added without deviating the
effect of the invention. According to the invention, the flame
retardant usually used in the common polyurethane foam and urethane
modified isocyanurate foam is effective and includes, for example,
halogenated organic phosphorus compounds such as
tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate,
tris(2,3-dichloropropyl)phosphate and the like; halogen compounds
such as chlorinated paraffin and the like; and inorganic flame
retardant such as antimony oxide and the like.
The urethane modified polyisocyanurate foams according to the
invention are obtained by the foaming reaction of the above
mentioned ingredients and have properties and thermal insulating
property substantially equal to those of the polyurethane foam and
further develop an improved fireproof property passed Grade 2
incombustibility according to JIS A-1321 combustion test.
Particularly, the followings are guessed with respect to the
improvement of the fireproof property.
Namely, an aspect of the invention lies in that the A-group diols
and B-group polyetherpolyols are used together in the defined
amount ranges as the modifying agent. Further, the A-group diols
are small in the compatibility with the organic polyisocyanate
owing to the large polarity, so that phase separation between the
resulting urethane bond and isocyanurate bond becomes good and as a
result, the formation of isocyanurate bond is hardly hindered in
the formation of urethane bond. While, the number of functional
group in the B-group polyetherpolyols is low, so that the molecular
chain in the formation of urethane bond is long and the crosslinked
density is low and as a result, the formation of isocyanurate bond
is hardly hindered. Therefore, the total effect of using the
A-group diols and B-group polyetherpolyols as the modifying agent
appears to perform the smooth formation of isocyanurate bond.
Moreover, the combination system of the alkali metal salt of
carboxylic acid with the amine catalyst (particularly, the
dialkylaminoalkyl phenols have a good compatibility with the
organic polyisocyanate and is effective for the formation of
isocyanurate bond), which has an excellent activity for the
formation of isocyanurate bond, is used as the isocyanate
trimerization catalyst, so that the formation of isocyanurate bond,
whose quantity and quality are superior to those of the
conventional modified isocyanurate foam, can be achieved by the
synergistic effect of the above modifying agent and catalyst
combination system.
However, when the total amount of the polyols used as the modifying
agent is below the lower limit, the quantity of urethane bond
formed in the initial reaction stage decreases and the reaction
system itself hardly reaches to an activation level required for
the formation of isocyanurate bond, so that the formation of
isocyanurate bond is suppressed. While, when the total amount
exceeds the upper limit, the quantity of urethane bond exhibiting
poor thermal resistance increases and the formation of isocyanurate
bond is apt to be hindered under influences of diffusion controlled
rate and the like accompanied with the increase of urethane bond
quantity. Moreover, when the weight ratio of the A-group diols to
the B-group polyetherpolyols is outside the defined range, the
balance between the urethane forming reaction and the isocyanurate
forming reaction becomes unbalanced, so that the formation of
isocyanurate bond is not achieved satisfactorily. Therefore, it is
guessed that when the total amount and weight ratio are outside the
defined ranges, the formation of isocyanurate bond exhibiting an
excellent thermal resistance is not sufficiently achieved so that
the fireproof property of the resulting foam is degraded.
Since the urethane modified polyisocyanurate foams according to the
invention has a sufficient quantity of isocyanurate bond, the
formation of char is accelerated on the surface of the foam
specimen in JIS A-1321 combustion test and the resulting char acts
as a barrier against a fire source to decrease the combustion
amount of the specimen as a whole, so that the heat release value,
fuming factor and the like lower and as a result, the improved
fireproof property capable of passing Grade 2 incombustibility is
obtained.
In FIG. 2 are shown an exhaust temperature curve and a fuming curve
of urethane modified polyisocyanurate foams of the invention and
the prior art according to JIS A-1321 surface combustion test,
respectively. The curve 1 represents an exhaust temperature of an
urethane modified polyisocyanurate foam obtained in Example 4 as
mentioned below, the curve 2 represents an exhaust temperature of
an urethane modified polyisocyanurate foam obtained in Comparative
Example 4 as mentioned below, the curve 3 represents an exhaust
temperature of a standard specimen (asbestos perlite plate defined
according to JIS A-5413), and the curves 4 and 5 represent fuming
quantities of the urethane modified polyisocyanurate foams of
Example 4 and Comparative Example 4, respectively. From FIG. 2, it
can be seen that in the urethane modified polyisocyanurate foam
according to the invention, the combustion is suppressed by the
formation of char barrier against the fire source and also the
exhaust temperature and fuming quantity become considerably lower
than those of the conventional urethane modified polyisocyanurate
foam.
The production of the foams according to the invention may be
carried out by any well-known processes, but is usually performed
as follows. That is, the polyols as an urethane modifying agent,
catalyst and blowing agent are mixed with stirring by adding a foam
stabilizer and other additives, if necessary, to form a homogeneous
mixed solution. To this solution is added the organic
polyisocyanate with stirring, and then the resulting reaction
mixture is extruded and foamed in a mold or the like by pouring,
spraying and the like.
The urethane modified polyisocyanurate foams according to the
invention are usable thermal insulating materials, building
materials or the like for housing, building and so on owing to the
improved fireproof property and thermal insulating property.
The following examples are given in illustration of the invention
with comparative examples and are not intended as limitations
thereof. In the examples, all parts and percents are by weight,
unless otherwise stated.
Moreover, the effect of the present invention is decided on a basis
of whether or not the foam passes Grade 2 incombustibility
according to JIS A-1321 combustion test. The surface test according
to JIS A-1321 is carried out by placing a test piece with a length,
width and thickness of 22 cm.times.22 cm.times.2.5 cm in a heating
furnace and then heating a surface of the test piece for a
predetermined period using gas as a sub-heat source and an electric
heater as a main heat source. Thereafter, the presence and degree
of crack/deformation, time of lingering flame after the completion
of heating, heat release value (temperature time area,
.degree.C.times.min.) calculated from the difference between the
exhaust temperature curve of the test piece and the reference curve
of perlite plate as a standard material, and fuming factor
calculated from maximum fuming quantity are measured to judge the
fireproof property of the test piece on a basis of acceptable
standard values shown in the following Table 1. Moreover, the
annexed test according to JIS A-1321 is usually carried out with
respect to unhomogeneous bodies such as laminates provided with
surface material and the like, which have a risk of burning that
portions exposed by jointing, screwing and the like in the firing,
but is always excluded in the homogeneous bodies such as the foams
according to the invention and the like. Therefore, the evaluation
by the annexed test is not omitted herein.
TABLE 1 ______________________________________ Test Acceptable
standard values of Grade 2 incombustib- ility (quasi-incombustible
material) according to JIS A-1321 combustion test Item Heat release
Time of value Fuming lingering Crack/ Class (.degree.C. .times.
min.) factor flame (sec.) deformation
______________________________________ Surface test not more not
more not more no harmful than 100 than 60 than 30 degree
______________________________________
EXAMPLES 1-6, COMPARATIVE EXAMPLES 1-2
An urethane modified polyisocyanurate foam was produced as follows
from a compounding recipe shown in the following Table 2, wherein
crude diphenylmethane diisocyanate (trade name: Sumidur 44V-20,
made by Sumitomo Bayer Urethane Co., Ltd., hereinafter abbreviated
as 44V-20) was used as an organic polyisocyanate, various amine
catalysts were used together with a solution of 33% potassium
acetate in diethylene glycol (hereinafter abbreviated as AcOK/DEG)
as an isocyanate trimerization catalyst, trichloromonofluoromethane
(hereinafter abbreviated as F-11) was used as a blowing agent, an
organopolysiloxane-polyoxyalkylene copolymer (trade name: L-5340,
made by Nippon Unicar Co., Ltd.) was used as a silicone surfactant,
and a combination of diethylene glycol (hereinafter abbreviated as
DEG) with polypropylene glycol (trade name: PP-2000, hydroxyl
equivalent=1,000, made by Sanyo Kasei Kogyo Co., Ltd.) was used as
a polyol of a modifying agent in a total amount of 17.17 parts by
weight (inclusive of diethylene glycol used as the solvent for
potassium acetate) per 100 parts by weight of the organic
polyisocyanate except that the weight ratio of DEG to PP-2000 was
changed.
In a polyethylene beaker were weighed and mixed the ingredients
other than the organic polyisocyanate, to which was added the
previously weighed organic polyisocyanate. Immediately after the
addition, the resulting foam forming composition was stirred at a
high speed for about 6 seconds and then poured and foamed in a
wooden mold. (The production of the foam was carried out at a scale
of three times of the quantities shown in Table 2. The other
examples as mentioned below were performed at the same scale.)
In Table 2 are shown the compounding recipe, foaming behavior and
evaluation results for Grade 2 incombustibility according to JIS
A-1321 combustion test with respect to the resulting urethane
modified polyisocyanurate foam.
TABLE 2(a)
__________________________________________________________________________
Com- Com- parative parative Example 1 Example 1 Example 2 Example 3
Example 4 Example 5 Example Example
__________________________________________________________________________
2 Compounding recipe 44V - 20 100 100 100 100 100 100 100 100
AcOK/DEG 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 DMP - 30 1) 0.5 0.5 0.5
0.5 -- -- 0.5 0.5 Polycat 41 2) -- -- -- -- 0.65 -- -- --
N,N-dimethylethanolamine -- -- -- -- -- 0.5 -- -- L-5340 1.0 1.0
1.0 1.0 1.0 1.0 1.0 1.0 F-11 20 20 20 20 20 20 20 20 DEG 16.37
13.38 10.30 8.8 8.8 8.8 5.6 2.4 PP-2000 -- 2.99 6.07 7.57 7.57 7.57
10.77 13.97 Weight ratio of low molecular weight diols to high
molecular .infin. 4.74 1.83 1.27 1.27 1.27 0.59 0.23 weight
polyether polyols Total amount of polyols used 17.17 17.17 17.17
17.17 17.17 17.17 17.17 17.17 NCO/OH 2.2 2.7 3.4 3.8 3.8 3.8 5.5
9.7 Foaming behavior cream time (sec.) 25 25 23 22 23 12 22 19 rise
time (sec.) 60 56 54 54 51 49 58 48
__________________________________________________________________________
TABLE 2(b)
__________________________________________________________________________
Comparative Example 1 Example 1 Example 2 Example 3 Example 4
Example 5 Example Example
__________________________________________________________________________
2 Foam density (g/cm.sup.3) 0.0273 0.0277 0.0288 0.0293 0.0282
0.0281 0.0316 0.0348 JIS-A-1321 combustion test heat release value
Td.theta. (.degree.C. .times. min.) 213.8 18.8 0 0 8.8 53.8 37.5
213.8 fuming factor C.sub.A 39.0 26.4 38.4 25.8 28.2 28.2 41.4 34.8
crack/deformation presence/ none/small none/small none/small
none/small none/small none/small presence/ large small time of
lingering flame (sec.) 14 0 8 10 3 26 25 31 judgement unaccept-
acceptable acceptable acceptable acceptable acceptable acceptable
unaccept- able able
__________________________________________________________________________
Note: 1 2,4,6tris(N,N-dimethylaminomethyl) phenol, made by Rohm
& Hass Co., Ltd 2
N,N',Ntris(dimethylaminopropyl)-sym-hexahydrotriazine, made by
Abbott Laboratories
As apparent from Table 2, the foams of Examples 1 to 6 satisfying
the definitions of polyols, catalyst, weight ratio of low molecular
weight diols/high molecular weight polyether polyols, total amount
of polyols used according to the invention pass Grade 2
incombustibility, while the foams of Comparative Examples 1 and 2
having the weight ratio outside the defined range are considerably
poor in the fireproof property and become unacceptable.
EXAMPLES 7-9, COMPARATIVE EXAMPLES 3-7
Urethane modified polyisocyanurate foams were produced under the
same conditions as described in Examples 1 to 6 from a compounding
recipe shown in the following Table 3 except that the isocyanate
trimerization catalyst was composed of an amine catalyst and a
solution of 20% potassium acetate in dipropylene glycol
(hereinafter abbreviated as AcOK/DPG), dipropylene glycol
(hereinafter abbreviated as DPG) was used as the low molecular
weight diol among the polyols used as the modifying agent, and the
weight ratio of DPG/PP-2000 was changed.
In Table 3 are shown the compounding recipe, foaming behavior and
evaluation results of the foam relating to Grade 2
incombustibility.
TABLE 3(a)
__________________________________________________________________________
Com- Com- Com- Com- Com- parative parative parative parative
parative Example 3 Example 7 Example 8 Example 9 Example 4 Example
5 Example Example
__________________________________________________________________________
7 Compounding recipe 44V - 20 100 100 100 100 100 100 100 100
AcOK/DPG 2.0 2.0 2.0 2.0 2.0 0.4 2.0 2.0 (potassium acetate alone)
DMP - 30 0.5 0.5 0.5 0.5 0.5 0.5 -- -- Polycat 41 -- -- -- -- -- --
0.5 -- N,N-dimethylethanolamine -- -- -- -- -- -- -- 0.5 L-5340 1.0
1.0 1.0 1.0 1.0 1.0 1.0 1.0 F-11 20 20 20 20 20 20 20 20 DPG 15.57
12.58 9.41 8.0 1.6 -- 9.41 9.41 PP-2000 -- 2.99 6.07 7.57 13.97
17.17 6.07 6.07 Weight ratio of low molecular weight diols to high
molecular .infin. 4.74 1.83 1.27 0.23 0 1.83 1.83 weight polyether
polyols Total amount of polyols used 17.17 17.17 17.17 17.17 17.17
17.17 17.17 17.17 NCO/OH 2.8 3.4 4.2 4.8 11.7 41.9 4.2 4.2
__________________________________________________________________________
TABLE 3(b)
__________________________________________________________________________
Com- Com- Com- Comparative parative parative parative Comparative
Example 3 Example 7 Example 8 Example 9 Example 4 Example 5 Example
Example
__________________________________________________________________________
7 Foaming behavior cream time (sec.) 21 21 21 20 16 25 23 25 rise
time (sec.) 55 70 65 71 58 120 67 63 Foam density (g/cm.sup.3)
0.0272 0.0284 0.0296 0.0292 0.0347 0.0357 0.0296 0.0304 JIS-A-1321
combustion test heat release value Td.theta. (.degree.C. .times.
min.) 218.8 70.0 70.0 77.5 260.0 290.0 180.0 217.5 fuming factor
C.sub.A 36.6 30.0 27.0 27.0 59.4 75.0 38.1 42.3 crack/deformation
none/medium none/small none/small none/small presence/ none/small
none/small small/small medium time of lingering flame (sec.) 0 14
10 15 86 16 0 0 judgement unaccept- acceptable acceptable
acceptable unaccept- unaccept- unaccept- unaccept- able able able
able able
__________________________________________________________________________
From the results of Table 3, it can be seen that even when using
the combination of DPG and PP-2000 as the polyol, if the weight
ratio of DPG/PP-2000 is outside the defined range according to the
invention, the resulting foams become unacceptable for Grade 2
incombustibility due to the significant increase of the heat
release value (Td.theta.), and that when using the catalyst other
than DMP-30 among the dialkylaminoalkyl phenols, the resulting
foams become unacceptable due to the fact that the heat release
value (Td.theta.) exceeds the standard value.
EXAMPLE 10, COMPARATIVE EXAMPLES 8-9
An urethane modified polyisocyanurate foam was produced under the
same conditions as described in Example 7 except that the weight
ratio of DPG/PP-2000 was 4.74 and the total amount of the polyols
used was changed.
In the following Table 4 are shown the compounding recipe, foaming
behavior and evaluation results of the foam relating to Grade 2
incombustibility.
TABLE 4 ______________________________________ Com- Comparative Ex-
parative Example 8 ample 10 Example 9
______________________________________ Compounding recipe 44V - 20
100 100 100 AcOK/DPG 2.0 2.0 2.0 DMP - 30 0.5 0.5 0.5 L-5340 1.0
1.0 1.0 F-11 20 20 20 DPG 5.49 9.81 22.51 PP-2000 1.50 2.41 5.08
Weight ratio of low molecular weight diols to high molecular weight
4.74 4.74 4.74 polyether polyols Total amount of polyols used 8.59
13.81 29.19 NCO/OH 6.8 4.25 2.0 Foaming behavior cream time (sec.)
24 22 23 rise time (sec.) 73 73 63 Foam density (g/cm.sup.3) 0.0290
0.0283 0.0297 JIS-A-1321 combustion test heat release value
Td.theta. (.degree.C. .times. min.) 180.0 77.5 243.8 fuming factor
C.sub.A 31.5 45.0 51.6 crack/deformation presence/ none/ presence/
small small medium time of lingering flame (sec.) 10 0 0 judgement
unacceptable accept- unacept- unaccept- able able
______________________________________
From the results of Table 4, it can be seen that when the total
amount of polyols used is outside the defined range according to
the invention as described in Comparative Examples 8 and 9, the
heat release value (Td.theta.) of the foams exceeds the standard
value, while the foam of Example 10 has a fireproof property passed
Grade 2 incombustibility with small deformation.
COMPARATIVE EXAMPLES 10-11
An urethane modified polyisocyanurate foam was produced under the
same conditions as described in Example 3 except that potassium
acetate and Polycat 41 were used alone as the isocyanate
trimerization catalyst.
In the following Table 5 are shown the compounding recipe, foaming
behavior and evaluation results of the foam relating to Grade 2
incombustibility.
TABLE 5 ______________________________________ Comparative
Comparative Example 10 Example 11
______________________________________ Compounding recipe 44V - 20
100 100 AcOK/DEG 1.2 -- Polycat 41 -- 3.0 L-5340 1.0 1.0 F-11 20 20
DEG 8.8 9.6 PP-2000 7.57 7.57 Weight ratio of low molecular weight
diols to high molecular 1.27 1.27 weight polyether polyols Total
amount of polyols used 17.17 17.17 NCO/OH 3.8 3.8 Foaming behavior
cream time (sec.) 74 20 rise time (sec.) 111 104 Foam density
(g/cm.sup.3) 0.0291 0.0312 JIS-A-1321 combustion test heat release
value Td.theta. (.degree.C. .times. min.) 158.8 220.8 fuming factor
C.sub.A 35.4 58.2 crack/deformation none/small none/small time of
lingering flame (sec.) 6 34 judgement unacceptable unacceptable
______________________________________
As apparent from Table 5, when potassium acetate as an alkali metal
salt of a carboxylic acid or Polycat 41 as an amine catalyst is
used alone, the resulting foam cannot pass Grade 2 incombustibility
due to the degradation of the fireproof property.
EXAMPLES 11-12, COMPARATIVE EXAMPLES 12-14
Urethane modified polyisocyanurate foams were produced under the
same conditions as described in Example 8 except that dipropylene
glycol was used as the low molecular weight diol, various
polypropylene glycols were used as the high molecular weight
polyether polyols, the weight ratio of dipropylene glycol to
polypropylene glycol was 1.83 and the total amount of these polyols
used was 17.17 parts by weight per 100 parts by weight of the
organic polyisocyanate.
In the following Table 6 are shown the compounding recipe, foaming
behavior and evaluation results of the foam relating to Grade 2
incombustibility.
TABLE 6(a)
__________________________________________________________________________
Comparative Comparative Comparative Example 11 Example 12 Example
12 Example 13 Example 14
__________________________________________________________________________
Compounding recipe 44V - 20 100 100 100 100 100 AcOK/DPG 2.0 2.0
2.0 2.0 2.0 DMP - 30 0.5 0.5 0.5 0.5 0.5 L-5340 1.0 1.0 1.0 1.0 1.0
F-11 20 20 20 20 20 DPG 9.41 9.41 9.41 9.41 9.41 PP-4000 (3) 6.07
-- -- -- -- PP-1200 (4) -- 6.07 -- -- -- PP-750 (5) -- -- 6.07 --
-- PP-400 (6) -- -- -- 6.07 -- PP-200 (7) -- -- -- -- 6.07 Weight
ratio of low molecular weight diols to high molecular 1.83 1.83
1.83 1.83 1.83 weight polyether polyols Total amount of polyols
used 17.17 17.17 17.17 17.17 17.17 NCO/OH 4.3 4.1 4.0 3.7 3.2
__________________________________________________________________________
TABLE 6(b)
__________________________________________________________________________
Comparative Comparative Comparative Example 11 Example 12 Example
12 Example 13 Example 14
__________________________________________________________________________
Foaming behavior cream time (sec.) 27 25 23 23 24 rise time (sec.)
75 68 62 62 70 Foam density (g/cm.sup.3) 0.0322 0.0300 0.0302
0.0287 0.0288 JIS-A-1321 combustion test heat release value
Td.theta. (.degree.C. .times. min.) 51.3 76.3 161.3 145.0 145.0
fuming factor C.sub.A 42.0 33.9 39.6 45.0 42.0 crack/deformation
none/small none/small none/small none/small none/small time of
lingering flame (sec.) 13 15 23 15 15 judgement acceptable
acceptable unacceptable unacceptable unacceptable
__________________________________________________________________________
Note: 3 Polypropylene glycol, hydroxyl equivalent 2000, made by
Sanyo Kasei Kogyo Co., Ltd. 4 Polypropylene glycol, hydroxyl
equivalent 600, made by Sanyo Kasei Kogy Co., Ltd. 5 Polypropylene
glycol, hydroxyl equivalent 375, made by Sanyo Kasei Kogy Co., Ltd.
Polypropylene glycol, hydroxyl equivalent 200, made by Sanyo Kasei
Kogyo Co., Ltd. Polypropylene glycol, hydroxyl equivalent 100, made
by Sanyo Kasei Kogyo Co., Ltd.
From the results of Table 6, it can be seen that when using
polypropylene glycols with a hydroxyl equivalent of less than 200,
the resulting foams become unacceptable for Grade 2
incombustibility because the heat release value (Td.theta.) exceeds
the standard value.
EXAMPLES 13-17, COMPARATIVE EXAMPLE 15
Urethane modified polyisocyanurate foams were produced under the
same conditions as described in Example 1 except that diethylene
glycol was used as the low molecular weight diol and various
polyether polyols were used as the high molecular weight polyether
polyol.
In the following Table 7 are shown the compounding recipe, foaming
behavior and evaluation results of the foam relating to Grade 2
incombustibility.
TABLE 7(a)
__________________________________________________________________________
Comparative Example 13 Example 14 Example 15 Example 15 Example 16
Example 17
__________________________________________________________________________
Compounding recipe 44V - 20 100 100 100 100 100 100 DEG 8.8 8.8 2.4
8.8 8.8 8.8 PE - 61 (8) 7.57 -- -- -- -- -- GP-3000 (9) -- 7.57
13.97 -- -- -- FA-103 (10) -- -- -- 7.57 -- -- FA-702 (11) -- -- --
-- 7.57 -- PTG-500 (12) -- -- -- -- -- 7.57 Weight ratio of low
molecular weight diols to high molecular 1.27 1.27 0.23 1.27 1.27
1.27 weight polyether polyols Total amount of polyois used 17.17
17.17 17.17 17.17 17.17 17.17 NCO/OH 3.8 3.8 9.7 3.9 3.9 3.8
Foaming behavior cream time (sec.) 20 26 25 8 22 33 rise time
(sec.) 50 65 63 34 55 75 Foam density (g/cm.sup.3) 0.0278 0.0289
0.0295 0.0306 0.0291 0.0279
__________________________________________________________________________
TABLE 7(b)
__________________________________________________________________________
Comparative Example 13 Example 14 Example 15 Example 15 Example 16
Example
__________________________________________________________________________
17 JIS-A-1321 combustion test heat release value Td.theta.
(.degree.C. .times. min.) 12.5 60.0 267.5 25.0 82.5 43.8 fuming
factor C.sub.A 30 32.4 35.1 36.0 33.0 32.1 crack/deformation
none/small none/small presence/medium none/small none/small
none/small time of lingering flame (sec.) 10 0 0 13 0 0 judgement
acceptable acceptable unacceptable acceptable acceptaable
acceptable
__________________________________________________________________________
Note: Common compounding conditions AcOK/DEG = 1.2 parts, DMP30 =
0.5 part, L5340 = 1.0 part, F11 = parts 8 polyoxyethylene
polyoxypropylene glycol, hydroxyl equivalent 900, made by Sanyo
Kasei Kogyo Co., Ltd. 9 polyoxypropylene triol, hydroxyl equivalent
1000, made by Mitsui Nisso Co., Ltd. 10 polyoxyethylene
polyoxypropylene triol, all of terminal hydroxyl group are primary
hydroxyl group, hydroxyl equivalent 1120, made by Sanyo Kasei Kogyo
Co., Ltd. 11 pentacrythritolbased polyoxyethylene polyoxypropylene
tetraol, hydroxy equivalent 1510, made by Sanyo Kasei Kogyo Co.,
Ltd. 12 polytetramethylene glycol, hydroxyl equivalent 1000, made
by Nippon Polyurethane Co., Ltd.
As apparent from Table 7, all of the foams in Examples 13 to 17
have a fireproof property passed Grade 2 incombustibility, while
the foam of Comparative Example 15 exhibits a considerable decrease
of the fireproof property.
EXAMPLES 18-23, COMPARATIVE EXAMPLES 16-29
Urethane modified polyisocyanurate foams were produced under the
same conditions as described in Example 1 except that PP-2000 was
used as the high molecular weight polyether polyol, and various
diol, triol and tetraol were used as the low molecular weight diol,
and potassium acetate used as the catalyst was dissolved in the
total amount of the diols used.
In the following Tables 8 to 10 are shown the compounding recipe,
foaming behavior and evaluation results of the foam relating to
Grade 2 incombustibility.
TABLE 8(a)
__________________________________________________________________________
Com- Com- parative Comparative Comparative parative Example 16
Example 18 Example 19 Example 20 Example 17 Example 18 Example
Example
__________________________________________________________________________
21 Compounding recipe 44V - 20 100 100 100 100 100 100 100 100
potassium acetate 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 F-11 15 20 20 20
20 16 20 20 ethylene glycol 5.39 -- -- -- -- -- -- -- DEG -- 9.22
-- -- -- -- -- -- triethylene glycol -- -- 13.05 -- -- -- -- --
tetraethylene glycol -- -- -- 16.88 -- -- -- -- PEG 200 (13) -- --
-- -- 17.40 -- -- -- 1,3-propane diol -- -- -- -- -- 6.61 -- --
propylene glycol -- -- -- -- -- -- 6.47 -- dipropylene glycol -- --
-- -- -- -- -- 7.57 PP-2000 6.96 6.96 6.96 6.96 6.96 6.96 10.70
6.96 Weight ratio of low molecular weight diols 0.77 1.32 1.88 2.43
2.50 0.95 0.60 1.09 to high molecular weight polyether Polyols
Total amount of polyols used 12.35 16.18 20.01 23.84 24.36 13.57
17.17 14.53
__________________________________________________________________________
TABLE 8(b)
__________________________________________________________________________
Comparative Comparative Comparative Comparative Example 16 Example
18 Example 19 Example 20 Example 17 Example 18 Example Example
__________________________________________________________________________
21 NCO/OH 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.8 Foaming behavior cream
time (sec.) 34 30 15 14 12 23 37 15 rise time (sec.) 60 70 52 56 41
56 85 76 Foam density (g/cm.sup.3) 0.0251 0.0293 0.0289 0.0267
0.0271 0.0308 0.0262 0.0292 JIS-A-1321 combustion test heat release
value Td.theta. (.degree.C. .times. min.) 146.3 33.8 16.3 88.8
215.0 137.5 236.25 77.5 fuming factor C.sub.A 39.0 34.5 39.0 27.6
36.0 45.0 37.8 27.0 crack/deformation none/medium none/small
none/small none/small presence/ none/small presence/ none/small
small medium time of lingering flame (sec.) 12 0 7 17 7 0 0 20
judgement unaccept- acceptable acceptable acceptable unaccept-
unaccept- unaccept- acceptable able able able able
__________________________________________________________________________
Note: Common compounding conditions DMP30 = 0.5 part, L5340 = 1.0
part (13) polyethylene glycol, hydroxyl equivalent 100, made by
Sanyo Kasei Kogyo Co., Ltd.
TABLE 9(a)
__________________________________________________________________________
Com- Com- Com- Com- Comparative Comparative parative parative
parative parative Example 20 Example 21 Example 21 Example 22
Example 22 Example 23 Example Example
__________________________________________________________________________
25 Compounding recipe 44V - 20 100 100 100 100 100 100 100 100
potassium acetate 0.8 0.8 0.8 0.8 0.4 0.4 0.4 0.4 F-11 20 20 20 20
20 20 20 20 1,4-butane diol 7.83 -- -- -- -- -- -- -- 1,3-butane
diol -- 7.83 -- -- -- -- -- -- 2,3-butane diol -- -- 7.83 -- -- --
-- -- 2-butene-1,4-diol -- -- -- 7.83 -- -- -- -- 1,5-pentane diol
-- -- -- -- 9.05 -- -- -- PP-200 -- -- -- -- -- 17.40 -- --
glycerin -- -- -- -- -- -- 9.60 -- trimethylol propane -- -- -- --
-- -- -- 7.78 PP-2000 6.96 6.96 6.96 6.96 6.96 6.96 7.57 6.96
Weight ratio of low molecular weight diols to high molecular weight
1.13 1.13 1.13 1.13 1.30 2.50 1.27 1.12 polyether polyols Total
amount of polyols used 14.79 14.79 14.79 14.79 16.01 24.36 17.17
14.74
__________________________________________________________________________
TABLE 9(b)
__________________________________________________________________________
Com- Com- parative parative Comparative Comparative Comparative
Comparative Example 20 Example 21 Example 21 Example 22 Example 22
Example 23 Example Example
__________________________________________________________________________
25 NCO/OH 4.0 4.0 4.0 4.0 4.0 4.0 3.4 4.0 Foaming behavior cream
time (sec.) 16 17 40 16 not foamed 50 not foamed 35 rise time
(sec.) 36 36 85 34 120 90 Foam density (g/cm.sup.3) 0.0324 0.0304
0.0280 0.0274 0.0297 0.0316 JIS-A-1321 combustion test heat release
value Td.theta. (.degree.C. .times. min.) 333.8 196.3 83.8 73.8
166.3 260.0 fuming factor C.sub.A 32.4 39.0 51.0 39.0 39.0 59.4 not
not crack/deformation none/small presence/ none/small none/small
measured none/small measured none/medium small time of lingering
flame (sec.) 0 0 0 0 0 42 judgement unaccept- unaccept- acceptable
acceptable unaccept- unaccept- able able able able
__________________________________________________________________________
TABLE 10(a)
__________________________________________________________________________
Comparative Comparative Comparative Comparative Example 26 Example
27 Example 28 Example 29
__________________________________________________________________________
Compounding recipe 44V - 20 100 100 100 100 potassium acetate 0.4
0.4 0.4 0.4 F-11 20 20 20 20 GP-250 (14) 14.44 -- -- -- AM-30 (15)
-- 9.6 -- -- Hyprox RQ-350 (16) -- -- 16.01 -- Newpol NP-300 (17)
-- -- -- 9.6 PP-2000 6.96 7.57 6.96 6.96 Weight ratio of low
molecular weight diols to high molecular 2.07 1.27 2.30 1.38 weight
polyether polyols Total amount of polyols used 21.40 17.17 22.97
16.56 NCO/OH 4.0 7.4 4.0 5.2 Foaming behavior cream time (sec.) 46
24 46 35 rise time (sec.) 105 135 115 90
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TABLE 10(b)
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Comparative Comparative Comparative Comparative Example 26 Example
27 Example 28 Example 29
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Foam density (g/cm.sup.3) 0.0305 0.0318 0.0336 0.0319 JIS-A-1321
combustion test heat release value Td.theta. (.degree.C. .times.
min.) 266.3 260.0 266.3 232.5 fuming factor C.sub.A 48.6 49.5 67.2
72.0 crack/deformation none/medium presence/small none/medium
presence/medium time of lingering flame (sec.) 0 0 29 33 judgement
unacceptable unacceptable unacceptable unacceptable
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14 polyoxypropylene triol, hydroxyl equivalent 83, made by Sanyo
Kasei Kogyo Co., Ltd. 15 polyoxyethylene triol, hydroxyl equivalent
106, made by Asahi Denka Kogyo Co., Ltd. 16 pentaerythritolbased
polyoxypropylene tetraol, hydroxyl equivalent 92, made by Dainippon
Ink Kagaku Kogyo Co., Ltd. 17 ethylendiaminebased polyoxypropylene
tetraol, hydroxyl equivalent 74, made by Sanyo Kasei Kogyo Co.,
Ltd.
From the results of Table 8, it can be seen that when diethylene
glycol, triethylene glycol, tetraethylene glycol, dipropylene
glycol, 2,3-butane diol and 2-butene-1,4-diol are used as the low
molecular weight diol, all of the resulting foams have a fireproof
property passed Grade 2 incombustibility, while when using diols
other than the above mentioned diols, triol and tetraol, the
fireproof property considerably lowers and the resulting foam
becomes unacceptable for Grade 2 incombustibility.
EXAMPLES 24-26
Urethane modified polyisocyanurate foams were produced in the same
manner as described in Example 1, except that a mixture of two
polyols was used as the high molecular weight polyether polyol in
Example 24, a mixture of two diols was used as the low molecular
weight diol in Example 25, and potassium n-caprylate was used as
the alkali metal salt of the carboxylic acid in Example 26.
In the following Table 11 are shown the compounding recipe, foaming
behavior and evaluation results of the foam relating to Grade 2
incombustibility.
TABLE 11 ______________________________________ Example 24 Example
25 Example 26 ______________________________________ Compounding
recipe 44V - 20 100 100 100 AcOK/DEG 1.2 1.2 -- potassium
n-caprylate/DEG 18 -- -- 1.2 DMP-30 0.5 0.5 0.5 L-5340 1.0 1.0 1.0
F-11 20 20 20 DEG 8.8 4.0 8.8 DPG -- 4.8 -- PP-2000 3.79 7.57 7.57
GP-3000 3.78 -- -- Weight ratio of low molecular weight diols to
high molecular weight 1.27 1.27 1.27 polyether polyols Total amount
of polyols used 17.17 17.17 17.17 NCO/OH 3.8 4.2 3.8 Foaming
behavior cream time (sec.) 25 20 25 rise time (sec.) 58 61 75 Foam
density (g/cm.sup.3) 0.0300 0.0303 0.0286 JIS-A-1321 combustion
test heat release value Td.theta. (.degree.C. .times. min.) 22.5
51.3 20.0 fuming factor C.sub.A 43.8 34.2 29.4 crack/deformation
none/small none/small none/small time of lingering flame (sec.) 15
0 0 judgement acceptable acceptable acceptable
______________________________________ Note:- 18 Solution of 33%
potassium ncaprylate in diethylene glycol (the amount of diethylene
glycol used as the solvent is also incorporated in the amount of
the low molecular weight diols used).
In any case, the resulting foams have a fireproof property passed
Grade 2 incombustibility as apparent from Table 9.
* * * * *